Non-wetting coating on a fluid ejector

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is the national stage of International Application Number PCT/US2009/062194, entitled “NON-WETTING COATING ON A FLUID EJECTOR”, filed on Oct. 27, 2009, which is based on and claims the benefit of the filing date of U.S. Provisional Application No. 61/109,754, entitled “NON-WETTING COATING ON A FLUID EJECTOR”, filed on Oct. 30, 2008.

TECHNICAL FIELD

This description relates to coatings on fluid ejectors.

BACKGROUND

A fluid ejector (e.g., an ink jet printhead) typically has an interior surface, an orifice through which fluid is ejected, and an exterior surface. When fluid is ejected from the orifice, the fluid can accumulate on the exterior surface of the fluid ejector. When fluid accumulates on the exterior surface adjacent to the orifice, further fluid ejected from the orifice can be diverted from an intended path of travel or blocked entirely by interaction with the accumulated fluid (e.g., due to surface tension).

Non-wetting coatings such as Teflon® and fluorocarbon polymers can be used to coat surfaces. However, Teflon® and fluorocarbon polymers typically are soft and are not durable coatings. These coatings also can be expensive and difficult to pattern.

SUMMARY

In one aspect, a fluid ejector includes a substrate having an exterior surface and an interior surface defining a flow path for fluid to an orifice in the exterior surface, and a non-wetting coating covering at least a portion of the exterior surface and substantially absent from the flow path. The non-wetting coating is formed of a molecular aggregation.

Implementations may include one or more of the following. An inorganic seed layer of different composition than the substrate may cover the interior surface and the exterior surface of the substrate, and the non-wetting coating may be disposed directly on the seed layer. The substrate may be formed of single crystal silicon and the seed layer may be silicon oxide. The non-wetting coating may be disposed directly on the substrate. The non-wetting coating includes molecules that have a carbon chain terminated at one end with a CF₃group. The non-wetting coating may include molecules formed from at least one precursor from the group consisting of tridecafluoro 1,1,2,2 tetrahydrooctyltrichlorosilane (FOTS) and 1H,1H,2H,2H perfluorodecyl-trichlorosilane (FDTS). The non-wetting coating may have a thickness between 50 and 1000 Angstroms. The non-wetting coating may include a plurality of identical molecules held in the molecular aggregation substantially by intermolecular forces and substantially without chemical bonds.

In another aspect, a method of forming a non-wetting coating on a fluid ejector includes holding a fluid ejector in a chamber at a first temperature, and flowing a precursor of the non-wetting coating into the chamber at a second temperature higher than the first temperature.

Implementations may include one or more of the following. A support in the chamber for holding the fluid ejector may be maintained at a lower temperature than a gas manifold for supplying the precursor gasses to the chamber. A temperature difference between the support and the gas manifold may be at least 70° C. The support may be cooled below room temperature and the gas manifold may be maintained at room temperature or higher. The support may be maintained at room temperature and the gas manifold may be heated above room temperature. The precursor may include at least of tridecafluoro 1,1,2,2 tetrahydrooctyltrichlorosilane (FOTS) or 1H,1H,2H,2H perfluorodecyl-trichlorosilane (FDTS). The non-wetting coating may be removed from an interior surface of the fluid ejector that defines a flow path for fluid ejection.

In another aspect, a fluid ejector includes a substrate having an exterior surface and an interior surface defining a flow path for fluid to an orifice in the exterior surface, a seed layer of different composition than the substrate coating at least the exterior surface of the substrate, and a non-wetting coating over the seed layer and covering at least a portion of the exterior surface and substantially absent from the flow path. The seed layer includes water molecules trapped in an inorganic matrix, and the seed layer includes an inner portion and an outer portion farther from the substrate than the inner portion, the outer portion having a higher concentration of water molecules than the inner portion.

Implementations may include one or more of the following. The seed layer may have a total thickness up to about 200 nm. The outer portion may have a thickness between about 50 and 500 Angstroms. The matrix of the seed layer may be an inorganic oxide. The inorganic oxide may be silicon dioxide. The non-wetting coating may include a siloxane bonded to the silicon dioxide. The seed layer may coat the inner surface.

In another aspect, a method of forming a non-wetting coating on a fluid ejector includes depositing a seed layer on an exterior surface of a substrate, the seed layer including water molecules trapped in an inorganic matrix, and depositing a non-wetting coating on the seed layer. Depositing the layer includes depositing an inner portion of the seed layer on the substrate at a first ratio of partial pressure water to partial pressure matrix precursor, and depositing an outer portion of the seed layer on the inner portion at a second ratio of partial pressure water to partial pressure matrix precursor that is higher than the first ratio.

Implementations may include one or more of the following. The inorganic matrix may be silicon dioxide. The substrate may be single-crystal silicon. The non-wetting coating may include a siloxane chemically bonded to the seed layer. The matrix precursor may includes SiCl₄. The first ratio H₂O:SiCl₄may be less than 2:1. The second ratio H₂O:SiCl₄may be more than 2:1. The outer portion may have a thickness of between about 50 and 500 Angstroms.

In another aspect, a fluid ejector includes a substrate having an exterior surface and an interior surface defining a flow path for fluid to an orifice in the exterior surface, a seed layer of different composition than the substrate coating at least a portion of the exterior surface of the substrate, and a non-wetting coating over the seed layer and covering at least a portion of the exterior surface and substantially absent from the flow path. The seed layer includes an inner portion with a first density and an outer portion farther from the substrate than the inner portion, the outer portion having a second density greater than the first density.

Implementations may include one or more of the following. The seed layer may include silicon dioxide. The substrate may be single-crystal silicon. The non-wetting coating may include a siloxane chemically bonded to the seed layer. The first density may be about 2.0 g/cm³. The second density may be at least 2.4 g/cm³, e.g., about 2.7 g/cm³. The second density may be at least about 0.3 g/cm³greater than the first density. The outer portion may have a thickness of about 40 Angstroms.

In another aspect, a method of forming a non-wetting coating on a fluid ejector includes depositing a seed layer on an exterior surface of a substrate, applying an oxygen plasma to the seed layer on the exterior surface, and depositing a non-wetting coating on the seed layer on the exterior surface.

Implementations may include one or more of the following. The seed layer may be deposited on an interior surface of the substrate that defines a flow path for fluid to an orifice in the exterior surface. The non-wetting coating may be deposited on the interior surface. The non-wetting coating on the interior surface may be removed. The seed layer may include silicon dioxide. The substrate may be single-crystal silicon. The non-wetting coating may include a siloxane that chemically bonds to the seed layer. At least a portion of the seed layer may be deposited at a ratio of partial pressure water to partial pressure matrix precursor that is greater than the ratio of water matrix consumed in the chemical reaction forming the silicon oxide. The matrix precursor may includes SiCl₄. The ratio of partial pressure water to partial pressure matrix precursor may be more than 2:1.

Certain implementations may have one or more of the following advantages. The exterior surfaces surrounding the orifice may be non-wetting, and interior surfaces that contact fluid to be ejected may be wetting. The non-wetting coating may reduce the accumulation of fluid on the exterior surface of the fluid ejector, and may thereby improve reliability of the fluid ejector. The non-wetting coating may be denser, which may make it more durable and insoluble to a wider range of fluids. A seed layer below the non-wetting coating may be denser, which may make it more durable and insoluble to wider range of fluids. The non-wetting coating may be thicker, and thus durability of the non-wetting coating can be improved. An overcoat layer may cover an interior surface of the fluid ejector. A highly wetting overcoat layer on surfaces contacting fluid to be ejected may enable improved control over droplet size, rate of ejection, and other fluid ejection properties.

DESCRIPTION OF DRAWINGS

<figref idrefs="DRAWINGS">FIG. 1A</figref> is a cross-sectional view of an exemplary fluid ejector.

<figref idrefs="DRAWINGS">FIG. 1B</figref> is an expanded view of the nozzle of the fluid ejector of <figref idrefs="DRAWINGS">FIG. 1A</figref>.

<figref idrefs="DRAWINGS">FIG. 2A</figref> is a schematic view of a non-wetting coating monolayer.

<figref idrefs="DRAWINGS">FIG. 2B</figref> is a schematic view of a non-wetting coating aggregation.

<figref idrefs="DRAWINGS">FIG. 2C</figref> is a schematic diagram of a chemical structure of an exemplary molecule of a non-wetting coating.

<figref idrefs="DRAWINGS">FIGS. 3A-3G</figref> illustrate an exemplary process for forming a fluid ejector.

<figref idrefs="DRAWINGS">FIG. 4</figref> is a cross-sectional view of a nozzle in another exemplary fluid ejector that does not includes a seed layer for the non-wetting coating.

<figref idrefs="DRAWINGS">FIG. 5A</figref> is a cross-sectional view of a nozzle in another exemplary fluid ejector that includes an overcoat layer.

<figref idrefs="DRAWINGS">FIG. 5B</figref> illustrates a step in an exemplary process for forming the fluid ejector shown in <figref idrefs="DRAWINGS">FIG. 5A</figref>.

DETAILED DESCRIPTION

<figref idrefs="DRAWINGS">FIG. 1A</figref> is a cross-sectional view of an fluid ejector <b>100</b> (e.g., an ink jet printhead nozzle), aspects of which not discussed herein can be implemented as described in U.S. Patent Publication No. 2008-0020573, the contents of which are hereby incorporated by reference.

The fluid ejector <b>100</b> includes a substrate <b>102</b> that has a fluid flow path <b>104</b> formed therein. The substrate <b>102</b> can include a flow-path body <b>110</b>, a nozzle layer <b>112</b> and a membrane layer <b>114</b>. The fluid flow path <b>104</b> can include a fluid inlet <b>120</b>, an ascender <b>122</b>, a pumping chamber <b>124</b> adjacent the membrane layer <b>114</b>, a descender <b>126</b> and a nozzle <b>128</b> formed through the nozzle layer <b>112</b>. The flow-path body <b>110</b>, nozzle layer <b>112</b> and membrane layer <b>114</b> can each be silicon, e.g., single crystal silicon. In some implementations, the flow-path body <b>110</b>, nozzle layer <b>112</b> and membrane layer <b>114</b> are fusion or silicon-to-silicon bonded to each other. In some implementations, the flow-path module <b>110</b> and the nozzle layer <b>112</b> are part of a monolithic body.

An actuator <b>130</b> is positioned on the membrane layer <b>114</b> over the pumping chamber <b>124</b>. The actuator <b>130</b> can include a piezoelectric layer <b>132</b>, a lower electrode <b>134</b> (e.g., a ground electrode), and an upper electrode <b>136</b> (e.g., a drive electrode). In operation the actuator <b>130</b> causes the membrane <b>114</b> over the pumping chamber <b>124</b> to deflect, pressurizing liquid (e.g., an ink, for example, a water-based ink) in the pumping chamber <b>124</b>, and causing the liquid to flow through the descender <b>126</b> and be ejected through the nozzle <b>128</b> in the nozzle layer <b>112</b>.

An inorganic seed layer <b>140</b> covers the outer surface of the nozzle layer <b>112</b> and the interior surfaces of the substrate <b>102</b> that define the flow-path <b>110</b>. Inorganic layer <b>140</b> may be formed of a material, e.g. an inorganic oxide, e.g., silicon oxide (SiO₂), that promotes adhesion of silane or siloxane coatings. The oxide layer can be between about 5 nm and about 200 nm thick. Optionally, as shown in <figref idrefs="DRAWINGS">FIG. 1B</figref>, an outer portion <b>142</b> of the inorganic layer <b>140</b> can have a higher density than the remainder of the inorganic layer <b>140</b>. For example, the outer portion <b>142</b> can have a density of 2.4 g/cm³or more (e.g., 2.7 g/cm³), whereas the inner portion can have a density of about 2.0 g/cm³. The outer portion <b>142</b> can have a thickness of no more than about 60 Angstroms, e.g., a thickness of about 40 Angstroms. The increased density of the outer portion of the seed can make it more durable and insoluble to a wider range of fluids. Alternatively, the inorganic layer <b>140</b> can have substantially the same density throughout.

Optionally, as shown in <figref idrefs="DRAWINGS">FIG. 1B</figref>, an outer portion <b>144</b> of the inorganic layer <b>140</b> can have a higher concentration of water trapped therein than the remainder of the inorganic layer <b>140</b>. The outer portion <b>144</b> can have a thickness of about 50 to 500 Angstroms. The increased water concentration can result in a higher concentration of —OH groups at the surface of the inorganic layer <b>140</b>, which can provide a higher concentration of attachment points for molecules of the non-wetting coating, which can produce a higher density in the non-wetting coating. However, the higher concentration of —OH groups at the surface of the inorganic layer <b>140</b> can also make the inorganic layer itself less chemically resistant. Alternatively, the inorganic layer <b>144</b> can have substantially the same water concentration throughout.

The outer portion <b>144</b> of high-water-concentration and the outer portion <b>142</b> of high density can be present individually or in combination.

A non-wetting coating <b>150</b>, e.g., a layer of hydrophobic material, covers the inorganic layer <b>140</b> on the exterior surface of the fluid ejector <b>100</b>, e.g., the non-wetting coating is not present in the flow-path <b>104</b>. As illustrated by <figref idrefs="DRAWINGS">FIG. 2A</figref>, the non-wetting coating <b>150</b> can a self-assembled monolayer, i.e., a single molecular layer. Such a non-wetting coating monolayer <b>150</b> can have a thickness of about 10 to 20 Angstroms, e.g., about 15 Angstroms. Alternatively, as illustrated by <figref idrefs="DRAWINGS">FIG. 2B</figref>, the non-wetting coating <b>150</b> can be a molecular aggregation. In a molecular aggregation, the molecules <b>152</b> are separate but held in the aggregation by intermolecular forces, e.g., by hydrogen bonds and/or Van der Waals forces, rather than ionic or covalent chemical bonds. Such a non-wetting coating aggregation <b>150</b> can have a thickness of about 50 to 1000 Angstroms. The increased thickness of the non-wetting coating make the non-wetting coating more durable and resistant to a wider range of fluids.

The molecules of the non-wetting coating can include one or more carbon chains terminated at one end with a —CF₃group. The other end of the carbon chain can be terminated with a SiCl₃group, or, if the molecule is bonded to a silicon oxide layer <b>140</b>, terminated with a Si atom which is bonded to an oxygen atom of the silicon oxide layer (the remaining bonds of the Si atom can be filled with oxygen atoms that are connected in turn to the terminal Si atoms of adjacent non-wetting coating molecules, or with OH groups, or both. In general, the higher the density of the non-wetting coating, the lower the concentration of such OH groups). The carbon chains can be fully saturated or partially unsaturated. For some of the carbon atoms in the chain, the hydrogen atoms can be replaced by fluorine. The number of carbons in the chain can be between 3 and 10. For example, the carbon chain could be (CH₂)_M(CF₂)_NCF₃, where M≧2 and N≧0, and M+N≧2, e.g., (CH₂)₂(CF₂)₇CF₃.

Referring to <figref idrefs="DRAWINGS">FIG. 2C</figref>, the molecules of the non-wetting coating adjacent the substrate <b>102</b>, i.e., the monolayer or the portion of the molecular aggregation adjacent the substrate, can be a siloxane that forms a bond with the silicon oxide of the inorganic layer <b>140</b>.

A process for forming the non-wetting coating on a fluid ejector (e.g., an ink jet printhead nozzle) begins, as shown <figref idrefs="DRAWINGS">FIG. 3A</figref>, with an uncoated substrate <b>102</b>. The uncoated substrate <b>102</b> can be formed of single-crystal silicon. In some implementations, a native oxide layer (a native oxide typically has a thickness of 1 to 3 nm) is already present on the surfaces of the substrate <b>102</b>.

The surfaces to be coated by the inorganic seed layer <b>140</b> can be cleaned prior to coating by, for example, applying an oxygen plasma. In this process, an inductively coupled plasma (ICP) source is used to generate active oxygen radicals which etch organic materials, resulting in a clean oxide surface.

As shown in <figref idrefs="DRAWINGS">FIG. 3B</figref>, the inorganic seed layer <b>140</b> is deposited on exposed surfaces of the fluid ejector, e.g. outer the nozzle layer <b>112</b> and the fluid flow path <b>104</b>, including the interior and exterior surfaces. An inorganic seed layer <b>140</b> of SiO₂can be formed on exposed surfaces of nozzle layer <b>112</b> and flow-path module <b>104</b> by introducing SiCl₄and water vapor into a chemical vapor deposition (CVD) reactor containing the uncoated fluid ejector <b>100</b>. A valve between the CVD chamber and a vacuum pump is closed after pumping down the chamber, and vapors of SiCl₄and H₂O are introduced into the chamber. The partial pressure of the SiCl₄can be between 0.05 and 40 Torr (e.g., 0.1 to 5 Torr), and the partial pressure of the H₂O can be between 0.05 and 20 Torr (e.g., 0.2 to 10 Torr). Seed layer <b>140</b> may be deposited on a substrate that is heated to a temperature between about room temperature and about 100° C. For example, the substrate might not be heated, but the CVD chamber can be at 35° C.

In some implementations of the CVD fabrication process, the seed layer <b>140</b> is deposited in a two-step process in which the ratios of partial pressure of H₂O to partial pressure of SiCl₄are different. In particular, in the second step that disposes the outer portion <b>144</b> of the seed layer, the partial pressure ratio of H₂O:SiCl₄can be higher than the ratio in the first step that disposes the portion of the seed layer closer to the substrate <b>102</b>. The first step can be performed at a higher partial pressure of H₂O: than the second step. In some implementations, in the first step the partial pressure ratio of H₂O:SiCl₄can be less than 2:1, e.g., about 1:1, whereas in the second step the partial pressure ratio of H₂O:SiCl₄can be 2:1 or more, e.g., 2:1 to 3:1. For example, the partial pressure of SiCl₄can be about 2 Torr in both steps, and the partial pressure of H₂O can be about 2 Torr in the first step and about 4-6 Torr in the second step. The second step can be conducted with sufficient duration so that the outer portion <b>144</b> has a thickness of about 50 to 500 Angstroms.

Without being limited to any particular theory, by performing the second deposition step at a higher partial pressure ratio of H₂O:SiCl₄, a higher concentration of H₂O is trapped in the SiO₂matrix in the outer portion <b>144</b>. As a result, a higher concentration of —OH groups can be present at the surface of the inorganic layer <b>140</b>.

Alternatively or in addition to performing the second deposition step at a higher partial pressure ratio of H₂O:SiCl₄, the second deposition step can be performed at a lower substrate temperature than the first step. For example, the first deposition step can be performed with the substrate at about 50-60° C., and the second deposition step at about 35° C. Without being limited to any particular theory, performing the second deposition step at a lower temperature should also increase the concentration of —OH groups present at the surface of the inorganic layer <b>140</b>.

In some implementations of the fabrication process, the entire seed layer <b>140</b> can be deposited in a single continuous step without varying the temperature or the higher partial pressure ratio of H₂O:SiCl₄. Again without being limited to any particular theory, this can result in the concentration of H₂O that is trapped in the SiO₂matrix being more uniform through the seed layer <b>140</b>.

The total thickness of the inorganic seed layer <b>140</b> can be between about 5 nm and about 200 nm. For some fluids to be ejected, the performance can be affected by the thickness of the inorganic layer. For example, for some “difficult” fluids, a thicker layer, e.g., 30 nm or more, such as 40 nm or more, e.g., 50 nm or more, will provide improved performance. Such “difficult” fluids can include, for example, various conducting polymers and light emitting polymers, e.g., poly-3,4-ethylenedioxythiophene (PEDOT), or a light emitting polymer, such as DOW Green K2, from Dow Chemical, as well as chemically “aggressive” inks, such as inks including “aggressive” pigments and/or dispersants.

Next, the fluid ejector can be subjected to an oxygen O₂plasma treatment step. In particular, both the inner and outer surfaces of the inorganic seed layer <b>140</b> are exposed to the O₂plasma. The oxygen plasma treatment can be conducted, for example, in anode coupling plasma tool from Yield Engineering Systems with an O₂flow rate of 80 sccm, a pressure of 0.2 Torr, an RF Power of 500 W, and a treatment time of five minutes.

Referring to <figref idrefs="DRAWINGS">FIG. 3C</figref>, the O₂plasma treatment can densify the outer portion <b>142</b> of the silicon oxide seed layer <b>140</b>. For example, the outer portion <b>142</b> can have a density of 2.4 g/cm³or more, whereas the lower portions of the seed layer <b>140</b> can have a density of about 2.0 g/cm³. In addition, the O₂plasma treatment can be even more effective at densification if the outer portion, e.g., outer portion <b>144</b>, was deposited at a “high” partial pressure ratio of H₂O:SiCl₄, e.g., at a pressure ratio of H₂O:SiCl₄greater than 2:1. In such a case, the outer portion <b>142</b> can have a density of about 2.7 g/cm³. The outer portion <b>142</b> can have a thickness of about 40 Angstroms.

Next, as shown in <figref idrefs="DRAWINGS">FIG. 3D</figref>, the non-wetting coating <b>150</b>, e.g., a layer of hydrophobic material, is deposited on exposed surfaces of the fluid ejector, including both the outer surface and the inner surface of the flow path <b>104</b>. The non-wetting coating <b>150</b> can be deposited using vapor deposition, rather than being brushed, rolled, or spun on.

The non-wetting coating <b>150</b> can be deposited, for example, by introducing a precursor and water vapor into the CVD reactor at a low pressure. The partial pressure of the precursor can be between 0.05 and 1 Torr (e.g., 0.1 to 0.5 Torr), and the partial pressure of the H₂O can be between 0.05 and 20 Torr (e.g., 0.1 to 2 Torr). The deposition temperature can be between room temperature and about 100 degrees centigrade. The coating process and the formation of the inorganic seed layer <b>140</b> can be performed, by way of example, using a Molecular Vapor Deposition (MVD)™ machine from Applied MicroStructures, Inc.

Suitable precursors for the non-wetting coating <b>150</b> include, by way of example, precursors containing molecules that include a terminus that is non-wetting, and a terminus that can attach to a surface of the fluid ejector. For example, precursor molecules that include a carbon chain terminated at one end with a —CF₃group and at a second end with an —SiCl₃group can be used. Specific examples of suitable precursors that attach to silicon surfaces include tridecafluoro-1,1,2,2-tetrahydrooctyltrichlorosilane (FOTS) and 1H,1H,2H,2H-perfluorodecyl-trichlorosilane (FDTS). Other examples of non-wetting coatings include 3,3,3-trifluoropropyltrichlorosilane (CF₃(CH₂)₂SiCl₃) and 3,3,3,4,4,5,5,6,6,-nonafluorohexyltrichlorosilane (CF₃(CF₂)₃(CH₂)₂SiCl₃). Without being limited by any particular theory, it is believed that when a precursor (such as FOTS or FDTS) whose molecules include an —SiCl₃terminus are introduced into the CVD reactor with water vapor, the precursor undergoes hydrolysis, and then a siloxane bond is created so that silicon atoms from the —SiCl₃groups bond with oxygen atoms from —OH groups on the inorganic layer <b>165</b>, resulting in a coating, such as a monolayer, of molecules with the other, i.e. non-wetting, terminus exposed.

In some implementations, the non-wetting coating <b>150</b> forms a self-assembled monolayer, i.e., a single molecular layer. Such a non-wetting coating monolayer <b>150</b> can have a thickness of about 10 to 20 Angstroms, e.g., about 15 Angstroms.

In some implementations, the non-wetting coating <b>150</b> forms a molecular aggregation, e.g., an aggregation of fluorocarbon molecules. Such a non-wetting coating aggregation <b>150</b> can have a thickness of about 50 to 1000 Angstroms. To form the non-wetting coating aggregation, the temperature of the substrate is set to be lower than the temperature of the non-wetting coating precursors. Without being limited to any particular theory, the lower temperature of the substrate effectively causing condensation of the fluorocarbon on the seed layer <b>140</b>. This can be accomplished by making the substrate support a lower temperature than the gas manifold, e.g., the lines or supply cylinders, for the gasses used to deposit the non-wetting coating. The temperature difference between the substrate support and the gas manifold (and possibly between the substrate itself and the gasses entering the chamber) can be about 70° C. For example, the substrate support can be cooled by liquid nitrogen, so that the substrate support is at about −194° C., while the gas manifold is at room temperature, e.g., about 33° C. As another example, the substrate support can be cooled by a chiller, so that the substrate support is at about −40° C., while the gas manifold is at room temperature, e.g., about 33° C. As another example, the substrate support is maintained at about room temperature, e.g., about 33° C., and the gas manifold is heated, e.g., to about 110° C.

The molecular aggregation can be formed from the precursors that would be used to form a monolayer, e.g., tridecafluoro-1,1,2,2-tetrahydrooctyltrichlorosilane (FOTS) and 1H,1H,2H,2H-perfluorodecyltrichlorosilane (FDTS).

Referring to <figref idrefs="DRAWINGS">FIG. 3E</figref>, a mask <b>160</b> is applied to an outer surface of the fluid ejector, e.g., at least a region surrounding nozzle <b>128</b>. The masking layer may be formed from various materials. For example, tape, wax, or photoresist can be used as a mask. Mask <b>160</b> protects the surface onto which it is applied from removal or damage resulting during a cleaning step (e.g. from exposure to oxygen plasma), and/or from subsequent deposition (e.g., from deposition of an overcoat layer). Mask <b>160</b> may have sufficiently low adhesion so that it may be removed without removing or damaging or otherwise materially altering non-wetting coating <b>150</b> beneath it.

Referring to <figref idrefs="DRAWINGS">FIG. 3F</figref>, the interior surfaces of the fluid ejector in the fluid path <b>104</b> are subjected to a cleaning step, for example a cleaning gas, e.g., an oxygen plasma treatment, that removes a portion of the non-wetting coating that is not covered by mask <b>160</b>. The oxygen plasma can be applied to a substrate inside a chamber, or the source of oxygen plasma can be connected to the inlet of the fluid path. In the former case, the mask <b>160</b> prevents the oxygen plasma in the chamber on the outside of the fluid ejector from removing the non-wetting coating on the exterior surface. In the later case, the mask <b>160</b> prevents the oxygen plasma from escaping through the orifices (and in this case, the mask need only cover the orifices themselves) and removing the non-wetting coating on the exterior surface.

Referring to <figref idrefs="DRAWINGS">FIG. 3G</figref>, following the cleaning step, the mask <b>160</b> is removed, to provide the fluid ejector as shown in <figref idrefs="DRAWINGS">FIGS. 1A and 1B</figref>. The final completed device is a fluid ejector with exterior surfaces that are non-wetting, and interior surfaces that are more wetting than the non-wetting surfaces.

In an exemplary process, the silicon oxide seed layer is deposited with a two-step process in which the second step is at a higher partial pressure ratio of H₂O:SiCl₄than the first step, e.g., with the second step at a partial pressure ratio H₂O:SiCl₄greater than 2:1. The seed layer on both the interior and exterior surfaces of the fluid ejector is then subjected to oxygen plasma treatment. The non-wetting coating is formed as a molecular aggregation on both the interior and exterior surfaces of the fluid ejector, and the interior surfaces are subjected to a further oxygen plasma treatment to remove the non-wetting coating from the interior surfaces, leaving the molecular aggregation on the exterior surface.

In another exemplary process, the silicon oxide seed layer is deposited with a single-step process with the second step at a “moderate” partial pressure ratio H₂O:SiCl₄, e.g., about equal to 2:1. The seed layer on both the interior and exterior surfaces of the fluid ejector is then subjected to oxygen plasma treatment. The non-wetting coating is formed as a monolayer, i.e., a single molecular layer, on both the interior and exterior surfaces of the fluid ejector, and the interior surfaces are subjected to a further oxygen plasma treatment to remove the non-wetting coating from the interior surfaces, leaving the non-wetting coating monolayer on the exterior surface.

In another implementation, as shown in <figref idrefs="DRAWINGS">FIG. 4</figref>, the fluid ejector <b>110</b> does not include a deposited seed layer <b>140</b>, and the non-wetting coating <b>150</b> is a molecular aggregation applied directly to the native surfaces of the fluid ejector (which might include a native oxide).

Referring to <figref idrefs="DRAWINGS">FIG. 5A</figref>, an overcoat layer <b>170</b> can be deposited on the inner surfaces of the fluid ejector, e.g., on the surfaces of the seed layer <b>140</b> that provide the fluid path, but not on the outer surface of the non-wetting coating <b>150</b>.

First, the cleaning step may not be completely effective in removing the non-wetting coating from the interior surface, particular in the region of the nozzles. However, the cleaning step is sufficiently effective that the subsequently deposited overcoat layer will adhere and cover the non-wetting that remains on the interior surface of the fluid ejector. Without being limited to any particular theory, the interior surface might be left with patches or regions of non-wetting coating and other patches or regions of exposed seed layer that are sufficiently large to permit adhesion of the overcoat layer, or the non-wetting on the interior surface might be damaged to permit adhesion of the overcoat layer.

Second, even if the cleaning step is sufficiently effective that the non-wetting coating <b>150</b> is completely removed from interior surfaces, if an outer portion of the seed layer <b>140</b> is deposited at high water vapor partial pressure, the surface of the outer portion of the inorganic layer <b>140</b> can have a higher concentration of —OH groups at the surface, which can make the inorganic layer more vulnerable to chemical attack by some liquids.

Fabrication of the fluid ejector as shown in <figref idrefs="DRAWINGS">FIG. 5A</figref> can proceed as discussed above with respect to <figref idrefs="DRAWINGS">FIGS. 3A-3F</figref>. However, referring to <figref idrefs="DRAWINGS">FIG. 5B</figref>, before the mask <b>160</b> is removed, the overcoat layer <b>170</b> is deposited on the exposed, e.g., unmasked, inner surfaces of the fluid ejector. After the overcoat layer <b>170</b> is deposited, the mask <b>160</b> can be removed. However, in some implementations, the material of the non-wetting coating can be such that the overcoat layer does not adhere to the non-wetting coating <b>150</b> during deposition (thus, the mask can be removed before deposition of overcoat layer, but the overcoat layer will not adhere to and not be formed on the non-wetting coating <b>150</b>).

The overcoat layer <b>170</b> provides an exposed surface, e.g., in the interior of the completed device, that is more wetting than the non-wetting coating <b>150</b>. In some implementations, overcoat layer <b>170</b> is formed from an inorganic oxide. For example, the inorganic oxide can include silicon, e.g., the inorganic oxide may be SiO₂. Overcoat layer <b>170</b> can be deposited by conventional means, such as CVD as discussed above. As noted above, a cleaning step, e.g., oxygen plasma, can be used to remove the non-wetting coating from the inner surfaces of the fluid ejector so that the overcoat layer will adhere to the inner surface. In addition, the same apparatus can be used to both clean surfaces to be deposited and to deposit the overcoat layer.

In some implementations, the overcoat layer <b>170</b> is deposited under the same conditions and have basically the same material properties, e.g., the same wettability, as the seed layer <b>140</b>. The overcoat layer <b>170</b> can be thinner than the seed layer <b>140</b>.

In some implementations, the overcoat layer <b>170</b> is deposited under different conditions and has different material properties from the seed layer <b>140</b>. In particular, the overcoat layer <b>170</b> can be deposited at a higher temperature or a lower water vapor pressure than the seed layer <b>140</b>. Thus, the surface of overcoat layer <b>170</b> can have a lower —OH concentration than surface of the seed layer <b>140</b>. Thus, the overcoat layer should be less subject to chemical attack by the liquid being ejected.

In some implementation, the overcoat layer <b>170</b> can also coat exposed surfaces of mask <b>160</b>, e.g., exposed interior and exterior surfaces. For instance, the fluid ejector <b>100</b> with mask attached can be placed in a CVD reactor into which precursors to overcoat layer <b>170</b>, e.g. SiCl₄and water vapor, are introduced. In such an implementation, the overcoat layer is formed on the exterior surface of the mask and the portion of the interior surface spanning the nozzle. The overcoat layers on the mask are then removed when the mask is removed from non-wetting coating <b>150</b>.

In alternative implementations, the overcoat layer <b>170</b> does not coat the exposed exterior surface of mask <b>160</b>, either because overcoat layer <b>170</b> is deposited only on interior surfaces, (e.g., the portion of the interior surface spanning the aperture) or because the overcoat layer does not physically adhere to the mask. The former case can be accomplished, for example, by equipping fluid ejector <b>100</b> with a suitable attachment so that precursors to overcoat layer <b>170</b> (e.g. SiCl₄and water vapor) are introduced only to interior exposed surfaces of the fluid ejector (i.e. surfaces that will contact fluid to be ejected from the fluid ejector). In these implementations, mask <b>160</b> may be applied to a sufficiently localized region surrounding nozzles <b>128</b> to prevent the overcoat layer from reaching exterior surface regions.

Optionally, following deposition of the overcoat layer <b>170</b>, the overcoat layer <b>140</b> can be subjected to an oxygen O₂plasma treatment step. In particular, the inner surfaces of the overcoat layer <b>170</b> are exposed to the O₂plasma. Without being limited to any particular theory, the O₂plasma treatment can densify the outer portion of the overcoat layer <b>170</b>. The oxygen plasma can be applied to the substrate inside a different chamber, e.g., with anode coupling plasma, than the one used to deposit the SiO₂layer.

In an exemplary process, the seed layer <b>140</b> is deposited at a higher partial pressure ratio of H₂O:SiCl₄, e.g., at a higher partial pressure of H₂O, than the overcoat layer <b>170</b>, but both the seed layer <b>140</b> and the overcoat layer <b>170</b> are subject to O₂plasma treatment.

In summary, in the final product, surfaces surrounding nozzle <b>128</b> (e.g., exterior surfaces) are non-wetting, and surfaces contacting fluid to be ejected (e.g., interior surfaces) are more wetting than surfaces coated with the non-wetting coating.

A number of implementations have been described. For example, the nozzle layer can be a different material than the flow-path body, and the membrane layer can similarly be a different material than the flow-path body. The inorganic seed layer can be sputtered rather than deposited by CVD. It will be understood that various other modifications may be made without departing from the spirit and scope of the invention.